By means of photochemical conversion of thin layers of a polymeric hexanoato aluminium complex as the precursor, thin aluminium oxide layers were prepared onto silicon wafers. The precursor compound was synthesized and characterized by several analytical techniques like NMR, FTIR, XPS, ICP, and found to be a polymeric aluminium-containing coordination compound which has been proposed to be a hydroxo-bridged aluminium chain with pendant hexanoyl side-chains ascertained as catena-poly [{di(kappa-O,O-hexanoato)aluminium}(mu-hydroxo)] (PHAH). Thin layers deposited from a solution of PHAH in toluene onto silicon wafers were irradiated using VUV radiation from a xenon excimer lamp. The layers were characterized by XPS, XRD, XRR, and spectroscopic ellipsometry. VUV radiation with a radiant exposure of E = 36J cm(-2) led to almost carbon-free amorphous layers with a composition close to that of alumina having a density of about 2.1 g cm(-3). Thus, using the example of a polymeric aluminium complex, the potential of the photochemical conversion of metal complexes into oxides could be shown as an alternative method, in addition to sol-gel techniques, for the generation of thin plane metal-oxide layers at normal temperature and pressure. (C) 2012 Elsevier B.V. All rights reserved.